Composite material containing graphene

ABSTRACT

In one aspect, a composite material is disclosed herein that includes graphene platelets dispersed in a matrix. In some cases, the graphene platelets are randomly oriented within the matrix. The composite material can provide improved thermal conductivity and may be formed into heat spreaders or other thermal management devices to provide improved cooling to electronic, electrical components and semiconductor devices.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of co-pending patentapplication Ser. No. 14/268,052 filed May 2, 2014, entitled COMPOSITEMATERIAL CONTAINING GRAPHENE, now allowed, which is incorporated hereinby referenced in its entirety.

FIELD

This disclosure relates generally to composite materials, and moreparticularly, to matrix composites comprising graphene nanoparticles.

BACKGROUND

Composite materials, also called composition materials or composites,are materials made from two or more constituent materials withsignificantly different physical and/or chemical properties. When thetwo or more constituent materials are combined, a material is producedwith characteristics different from the individual components. The newmaterial may be preferred for many reasons. Common examples includematerials which are stronger, lighter or less expensive when compared totraditional materials.

Graphene includes sp²-bonded carbon as a primary carbon component, asopposed to sp³-bonded carbon. For example, a graphene sheet is aone-atom-thick planar sheet of sp²-bonded carbon atoms that are denselypacked in a honeycomb crystal lattice. Graphene-based materials havebeen combined with other materials to form composites, but some suchcomposites can be tedious and/or expensive to manufacture. In addition,some such composites can exhibit one or more properties that are notsuitable for some applications. Therefore, improved graphene-containingcomposite materials are needed.

SUMMARY

According to one aspect of the present disclosure, a composite materialcomprises a matrix and graphene particles dispersed within the matrix,wherein the graphene particles are randomly oriented in the matrix. Sucha composite material can provide improved thermal conduction propertiesand/or improved ease of fabrication compared to some other compositematerials, including other composite materials used for thermalmanagement applications.

According to a further aspect, the matrix is thermally conductive, andcomprises a metal. In a still further variation, the matrix comprises oris formed from a metal selected from the group including aluminum,aluminum alloys, copper, copper alloys, titanium, titanium alloys,stainless steel, brass, and combinations thereof. In some cases, thematrix comprises or is formed from a polymeric material, such as athermoset polymeric material or a thermoplastic polymeric material.

Moreover, in some implementations, the graphene particles of a compositematerial described herein are provided as a plurality of grapheneplatelets, and the composite comprises from about 1 volume % to about 40volume % or from about 1 volume % to about 20 volume % graphene, basedon the total volume of the composite. In a further aspect, the grapheneplatelets have an average thickness of about 0.3 nm to about 1 nm, about1 nm to about 100 nm, about 1 nm to about 10 nm, about 1 nm to about 300nm, or about 1 nm to about 1000 nm.

In another aspect, the present disclosure is directed to a thermallyconductive material comprising or formed from a composite materialdescribed herein. Still further, the present disclosure is directed tothermally conductive components including thermally conductive materialscomprising or formed from a composite material described herein. In someimplementations, the thermally conductive component is a heat spreader,a heat sink, or another thermal management component. Thus, the presentdisclosure is also directed to thermal management and thermal conductionapplications.

Other features and advantages of the present disclosure will be apparentfrom the following more detailed description of variations, taken inconjunction with the accompanying drawing that illustrate, by way ofexample, the principles of the disclosure.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 illustrates an exemplary graphene sheet according to oneimplementation described herein.

DETAILED DESCRIPTION

Implementations described herein can be understood more readily byreference to the following detailed description, examples, and drawing.Elements, apparatus, and methods described herein, however, are notlimited to the specific implementations presented in the detaileddescription, examples, and drawing. It should be recognized that theseimplementations are merely illustrative of the principles of the presentdisclosure. Numerous modifications and adaptations will be readilyapparent to those of skill in the art without departing from the spiritand scope of the disclosure.

In addition, all ranges disclosed herein are to be understood toencompass any and all subranges subsumed therein. For example, a statedrange of “1.0 to 10.0” should be considered to include any and allsubranges beginning with a minimum value of 1.0 or more and ending witha maximum value of 10.0 or less, e.g., 1.0 to 5.3, or 4.7 to 10.0, or3.6 to 7.9.

All ranges disclosed herein are also to be considered to include the endpoints of the range, unless expressly stated otherwise. For example, arange of “between 5 and 10” should generally be considered to includethe end points 5 and 10.

Further, when the phrase “up to” is used in connection with an amount orquantity, it is to be understood that the amount is at least adetectable amount or quantity. For example, a material present in anamount “up to” a specified amount can be present from a detectableamount and up to and including the specified amount.

In one aspect, composite materials are described herein. In someimplementations, a composite material comprises, consists, or consistsessentially of a matrix and graphene platelets dispersed in the matrix,wherein the graphene platelets are randomly oriented in the matrix.

Turning now to specific components of composite materials, compositematerials described herein comprise a matrix. In some cases, the matrixis thermally conductive. Moreover, a matrix can comprise or be formedfrom any material not inconsistent with the objectives of the presentdisclosure. For example, in some cases, a matrix comprises or is formedfrom a metal. Any metal not inconsistent with the objectives of thepresent disclosure may be used. In some implementations, the matrix of acomposite material described herein comprises or is formed from a metalselected from the group consisting of aluminum, aluminum alloys, copper,copper alloys, titanium, titanium alloys, stainless steel, brass, andcombinations thereof.

In some instances, a matrix comprises or is formed from a non-metalmaterial, such as a polymeric material. Any polymeric material notinconsistent with the objectives of the present invention may be used.In some cases, a polymeric material is selected from the groupconsisting of a thermoset material and a thermoplastic material. In someimplementations, a matrix comprises or is formed from a polycarbonate, apolyethylene such as a high-density polyethylene, a polypropylene, apolyvinyl chloride (PVC), an acrylonitrile butadiene styrene (ABS)polymer, a maleimide or bismaleimide, a phenol formaldehyde polymer, apolyepoxide, a polyether ether ketone (PEEK) polymer, a polyetherimide(PEI), a polyimide, a polysulfone, or a combination of one or more ofthe foregoing.

Moreover, in some instances, the matrix of a composite materialdescribed herein comprises or is formed from one or more glass, ceramicor other refractory material, and carbon. A matrix can also comprise orbe formed from a combination of a metal, polymeric material, glassmaterial, ceramic material, and carbon material.

Composite materials described herein also comprise graphene particlesdispersed in the matrix of the composite. Any graphene particles notinconsistent with the objectives of the present disclosure may be used.According to the present disclosure, one exemplary graphene particle isa one-atom thick planar sheet of sp²-bonded carbon atoms that aredensely packed in a honeycomb crystal lattice.

Graphene particles of a composite material described herein can have anysize and shape not inconsistent with the objectives of the presentdisclosure. In some cases, for instance, graphene particles have ananisotropic shape, such as a rod or needle shape or a platelet shape. Insome implementations, graphene particles comprise graphene platelets,nanosheets, or nanoplatelets formed from one or more atomic layers ofgraphene. Thus, in some implementations, a graphene particle describedherein comprises, consists, or consists essentially of one or moregraphene sheets. A graphene sheet, in some implementations, comprises asingle molecular or atomic layer having a flat planar structure. Anynumber of graphene sheets not inconsistent with the objectives of thepresent disclosure may be used. In some implementations, a grapheneparticle comprises a plurality of graphene sheets. The plurality ofgraphene sheets, in some implementations, can be arranged in a randomlystacked or layered configuration. In other implementations, a grapheneparticle comprises or consists of a single randomly oriented graphenesheet. Therefore, in some implementations, a graphene particle describedherein comprises 1 or more atomic layers of graphene. In someimplementations, a graphene particle comprises between 1 and 10 atomiclayers of graphene. In some implementations, a graphene particlecomprises between 1 and 5 atomic layers or between 1 and 3 atomic layersof graphene. In other instances, a graphene particle comprises between 1and 1000 atomic layers, between 1 and 500 atomic layers of graphene, orbetween 1 and 100 atomic layers of graphene.

Further, in some implementations comprising graphene platelets, theplatelets have an average thickness of up to about 1000 nm or up toabout 100 nm. In some instances, graphene platelets have an averagethickness of about 0.3 nm to about 1 nm, about 1 nm to about 1000 nm,about 1 nm to about 100 nm, about 1 nm to about 10 nm, or about 300 nmto about 1000 nm. Moreover, in some cases, such graphene platelets havean average length and/or width of up to about 1 μm, up to about 1 cm, orup to about 5 cm. In some instances, graphene platelets or othergraphene particles have an average length and/or an average widthbetween about 1 μm and about 5 cm, between about 1 μm and about 1 cm,between about 1 μm and about 500 μm, between about 1 μm and about 100μm, between about 1 μm and about 10 μm, between about 5 μm and about 1cm, between about 5 μm and about 500 μm, between about 5 μm and about100 μm, between about 10 μm and about 1 cm, between about 10 μm andabout 500 μm, between about 10 μm and about 100 μm, between about 50 μmand about 1 cm, between about 100 μm and about 1 cm, or between about100 μm and about 500 μm.

Additionally, in some implementations, anisotropic graphene particleshave a random orientation within the matrix of a composite materialdescribed herein. For example, in some cases, the graphene is providedas a plurality of randomly oriented graphene platelets. A “random”orientation, for reference purposes herein, is relative to the directionof a unique axis of the anistropic particles. In some implementations,for instance, a random orientation comprises an orientation in which theZ axes of the particles are randomly oriented in three-dimensionalspace, where the Z axis of a particle can correspond to the thickness ofthe particle, as opposed to the length or width of the particle. Thus,randomly oriented particles can be contrasted with oriented or alignedparticles. However, it is also possible for the graphene particles of acomposite material described herein to have an aligned orientationwithin the matrix of the composite material.

FIG. 1 illustrates a graphene nanoplate 10 according to one aspect ofthe present disclosure. As can be seen in FIG. 1, the graphenenanoplatelet 10 has a length (L) along the X axis, a width (W) along theY axis and a thickness or height (H) along the Z axis. In other words,the L and W of the nanoplate 10 lie oriented and/or aligned in the X-Yplane. Ordinarily, the L and W are the major dimensions of graphenenanoplatelet 10 and the graphene nanoplatelet is predominantly orientedand/or aligned in the X-Y plane. However, according to the presentdisclosure, it has now been shown that graphene has displayed beneficialand unexpected performance properties when it is presented in a randomorientation. According to one variation, the L and W may be about 1 μmto about 1 cm. In another aspect, the L and W may be from about 5 μm toabout 10 mm. In another aspect, the graphene nanoplatelets 10 have anaverage H of from about 1 to about 10 atomic layers. Additionally, inone aspect, graphene nanoplatelets 10 have a rectangular geometry in theX-Y plane, or may have other geometries including, but not limited tosquare, oval, hexagonal, or other polygonal geometries. Further, astechnology develops, the present disclosure contemplates larger andsmaller graphene platelet dimensions.

According to the present disclosure, graphene platelets, in someimplementations, can have a thermal conductivity of about 5,300 (W/mK)in the X-Y plane. Incorporating such graphene platelets into or onto asubstrate material can improve the thermal conductivity of the substratematerial. According to one aspect, the graphene platelets are preferablydistributed within a substrate material, such as, for example, amaterial matrix, to produce a composite material having an increasedthermal conductivity across in one or more dimensions.

Graphene particles described herein can be present in a compositematerial in any amount not inconsistent with the objectives of thepresent disclosure. In some cases, for instance, the composite materialcomprises graphene particles in an amount of from about 1 volume % toabout 90 volume %, based on the total volume of the composite material.In another variation, the matrix material comprises graphene particlesin an amount of from about 1 volume % to about 60 volume %, about 1volume % to about 40 volume %, about 1 volume % to about 20 volume %, orabout 1 volume % to about 10 volume %. In yet another variation, thematrix material comprises graphene particles in an amount of from about5 volume % to about 30 volume % or about 5 volume % to about 20 volume%. In still another variation, the matrix material comprises grapheneparticles in an amount of from about 5 volume % to about 10 volume %. Ina further variation, the matrix material comprises graphene particles inan amount of from about 1 volume % to about 5 volume %. In addition, insome cases, the amount of graphene dispersed in a matrix described herein selected based on the thermal conductivity of the matrix and/or adesired thermal conductivity of the composite material. For example, insome instances, a higher amount of graphene is added to a matrixmaterial having a lower thermal conductivity. In particular, in someimplementations comprising a non-conductive or minimally conductivematrix material such as some polymeric matrix materials describedherein, graphene particles are dispersed in the matrix in an amountabove the percolation limit. In some implementations, graphene particlesdispersed in the matrix in an amount above the percolation limit arepresent in a concentration sufficiently high to provide a continuousnetwork of graphene particles within the matrix. Such a continuousnetwork can be formed by graphene particles in direct physical contactwith one another. Similarly, in other cases, rather than using a higheramount of graphene, a lower amount of graphene can be added to a matrixmaterial having a higher thermal conductivity.

Moreover, in some implementations, the size, shape, and volume % ofgraphene particles in a matrix described herein are selected to have aminimal impact on the mechanical properties and/or processibility of thematrix material. For example, in some cases, graphene platelets having athickness of up to about 10 nm, a width of up to about 100 mm, and alength of up to about 1 cm are used in an amount up to about 20 volume%. In some such instances, the tensile strength and/or tensile modulusof the matrix material is altered by less than about 20%, less thanabout 15%, less than about 10%, or less than about 5% by the inclusionof the graphene platelets, based on the tensile strength and/or tensilemodulus of the matrix material without any graphene platelets. Thetensile strength and/or tensile modulus of a matrix or compositematerial can be measured in any manner not inconsistent with theobjectives of the present disclosure. In some cases, the tensilestrength and/or tensile modulus is measured by ASTM D3552 or ASTM E8. Insome implementations, the Charpy impact and/or ductile-brittletransition temperature (DBTT) of the matrix material is altered by lessthan about 15%, less than about 10%, less than about 5%, or less thanabout 1% by the inclusion of the graphene platelets, based on the Charpyimpact and/or DBTT of the matrix material without any grapheneplatelets. The Charpy impact and/or DBTT of a matrix or compositematerial can be measured in any manner not inconsistent with theobjectives of the present disclosure. In some cases, the Charpy impactand/or DBTT is measured by a four-point bending test at a range oftemperatures or in a manner according to ASTM A370 and/or ASTM E23.

A composite material described herein can be manufactured in any mannernot inconsistent with the objectives of the present disclosure,including the following exemplary processes. In one process, grapheneparticles such as graphene platelets are provided in a dry form or in adispersed form in a solvent. If provided in a solvent, the grapheneparticles can be dispersed in a solvent having a low boiling point suchas, for example, acetone, alcohol, or a similar solvent. The grapheneparticles are then introduced to a thin metal or polymeric mesh or otherporous network, including an isotropic or randomly oriented mesh ornetwork. The graphene particles are captured on or within the mesh ornetwork, and the solvent is removed by heating to form the compositematerial. In one variation, the mesh or network is formed from a metalsuch as aluminum, aluminum alloy, copper, copper alloy, titanium,titanium alloy, stainless steel, brass, or a combination thereof. Ifdesired, the process may be repeated with multiple layers stacked toform a composite building block. According to one variation, thecomposite block may be further hot and/or cold worked to reach a desiredthickness and density. Shaping may then be performed by any method toachieve a desired shape.

In another variation, the graphene composite can be formed by hotmelting and/or extruding a graphene/matrix mixture. According to anothervariation, a graphene composite is formed by forming graphene layers ina loosely connected thin sheet form with a metal matrix by hot melt orelectrolytic/electrolysis plating to form a composite building block.The composite building blocks can then be processed as described aboveif desired. For example, the composite building blocks can be stacked,hot pressed, cold formed and/or machined/shaped. In a furtherimplementation, graphene-containing composites may be formed usingrandomly oriented graphene sheets and conventional powder metallurgicalprocessing.

In another aspect, thermally conductive materials are described herein.Such a thermally conductive material comprises a composite materialdescribed herein. Any composite material described hereinabove may beused. Similarly, in another aspect, thermally conductive components aredescribed herein. Such a component can include a thermally conductivematerial comprising a composite material described herein. Further, thecomponent can have any form or be used for any purpose not inconsistentwith the objectives of the present disclosures. In some cases, forinstance, a thermally conductive component is a heat spreader, a heatsink, or other thermal management component. Thus, the presentdisclosure is also directed to thermal management and thermal conductionapplications. In some implementations, for example, methods of thermallymanaging a heat-generating component such as an electronic component aredescribed herein. In some cases, such a method comprises contacting athermally conductive material described herein and a heat-generatingcomponent, and transferring thermal energy from the heat-generatingcomponent to the thermally conductive material. Moreover, in someimplementations, the method further comprises dissipating thetransferred thermal energy, including by means of conduction coolingwith a fluid such as air or a liquid coolant. Thermal energy transferredto the thermally conductive material can also be dissipated in otherways.

The following Example illustrates one use for graphene-containingcomposite materials disclosed herein; namely, the use of such compositematerials to provide thermal management for electronic components.

EXAMPLE Composite Materials

Graphene-containing composite materials according to someimplementations described herein are formed by extrusion of either (1) amixture of aluminum and graphene platelets or (2) a mixture of acomposite plastic material (graphite-reinforced plastic) and grapheneplatelets. The graphene platelets have a random orientation within thealuminum or composite material matrix. The loading of graphene plateletsis 10 volume %, based on the total volume of the composite material. Thecomposite materials are then formed into heat spreaders for use with anelectronic component. The thermal conduction properties of the compositematerials are compared to the thermal conduction properties of heatspreaders having the same form factor but formed from (3) a mixture ofaluminum with aluminum plates dispersed in the aluminum matrix or (4)aluminum plates dispersed in the graphite-reinforced plastic. Thealuminum plates have the same dimensions and loading as the grapheneplatelets. The four heat spreaders (experimental heat spreaders (1) and(2) and comparative heat spreaders (3) and (4)) are then used forconduction cooling of an electronic device. The peak temperature of thedevice is then measured as a function of time for each heat spreader. Itwas found that heat spreaders formed from a composite material describedherein provide improved results compared to heat spreaders that do notinclude graphene platelets. For example, heat spreader (1) provides adevice temperature about 10-15° C. lower than heat spreader (3) at timepoints between about 500 and 600 seconds, corresponding to a temperaturereduction of about 9 to 14%, where the percentage is based on thetemperature difference divided by the temperature provided by heatspreader (3).

Various implementations of the disclosure have been described infulfillment of the various objectives of the disclosure. It should berecognized that these implementations are merely illustrative of theprinciples of the present disclosure. Numerous modifications andadaptations thereof will be readily apparent to those skilled in the artwithout departing from the spirit and scope of the disclosure.

That which is claimed is:
 1. A composite material comprising: apolymeric matrix; and a plurality of graphene platelets dispersed in thepolymeric matrix; wherein the graphene platelets are randomly orientedin the polymeric matrix.
 2. The composite material of claim 1, whereinthe polymeric matrix comprises one or more of a thermoset material or athermoplastic material.
 3. The composite material of claim 1, whereinthe polymeric matrix comprises one or more of a polycarbonate, apolyethylene, a high-density polyethylene, a polypropylene, a polyvinylchloride (PVC), an acrylonitrile butadiene styrene (ABS) polymer, amaleimide, a bismaleimide, a phenol formaldehyde polymer, a polyepoxide,a polyether ether ketone (PEEK) polymer, a polyetherimide (PEI), apolyimide, a polysulfone, or a combination thereof.
 4. The compositematerial of claim 1, wherein the graphene platelets have an averagethickness of about 1 nm to about 1000 nm.
 5. The composite material ofclaim 1, wherein the graphene platelets have an average thickness ofabout 1 nm to about 10 nm.
 6. The composite material of claim 1, whereinthe graphene platelets have an average thickness of about 0.3 nm toabout 1 nm.
 7. The composite material of claim 4, wherein the grapheneplatelets have an average length and/or width of about 1 μm to about 5cm.
 8. The composite material of claim 5, wherein the graphene plateletshave an average length and an average width of about 1 μm to about 1 cm.9. The composite material of claim 1, wherein the composite materialcomprises the graphene platelets in an amount of from about 1% to about40% by volume, based on the total volume of the composite material. 10.The composite material of claim 1, wherein the composite materialcomprises the graphene platelets in an amount of from about 1% to about20% by volume, based on the total volume of the composite material. 11.The composite material of claim 1, wherein the composite materialexhibits a ductile-brittle transition temperature within about 15% ofthe ductile-brittle transition temperature of the polymeric matrixwithout any graphene platelets.
 12. The composite material of claim 1,wherein the composite material exhibits a tensile strength within about20% of the tensile strength of the polymeric matrix without any grapheneplatelets.
 13. The composite material of claim 1, wherein: the plateletshave an average thickness of about 1 nm to about 10 nm, an averagelength of about 1 um to about 5 cm, and an average width of about 1 umto about 5 cm; and the composite material comprises the grapheneplatelets in an amount of from about 1% to about 20% by volume, based onthe total volume of the matrix.
 14. The composite material of claim 13,wherein the composite material exhibits a ductile-brittle transitiontemperature within about 15% of the ductile-brittle transitiontemperature of the polymeric matrix without any graphene plateletsand/or a tensile strength within about 20% of the tensile strength ofthe polymeric matrix without any graphene platelets.
 15. The compositematerial of claim 1, wherein: the graphene platelets have an averagethickness of about 0.3 nm to about 1 nm, an average length of about 1 μmto about 1 cm, and an average width of about 1 μm to about 1 cm; and thecomposite material comprises the graphene platelets in an amount of fromabout 1% to about 20% by volume, based on the total volume of thematrix.
 16. The composite material of claim 15, wherein the compositematerial exhibits a ductile-brittle transition temperature within about15% of the ductile-brittle transition temperature of the polymericmatrix without any graphene platelets and/or a tensile strength withinabout 20% of the tensile strength of the polymeric matrix without anygraphene platelets.
 17. A thermally conductive material comprising thecomposite material of claim
 1. 18. A thermally conductive componentcomprising the thermally conductive material of claim
 17. 19. Thethermally conductive component of claim 18, wherein the component is aheat spreader or a heat sink.
 20. A method of thermally managing aheat-generating component comprising: contacting a thermally conductivematerial with a heat-generating component; and transferring thermalenergy from the heat-generating component to the thermally conductivematerial, wherein the thermally conductive material comprises acomposite material comprising a matrix; and a plurality of grapheneplatelets dispersed in and randomly oriented in the matrix.